US3589908A - Photographic materials containing hydrophilic colloids - Google Patents
Photographic materials containing hydrophilic colloids Download PDFInfo
- Publication number
- US3589908A US3589908A US506831A US3589908DA US3589908A US 3589908 A US3589908 A US 3589908A US 506831 A US506831 A US 506831A US 3589908D A US3589908D A US 3589908DA US 3589908 A US3589908 A US 3589908A
- Authority
- US
- United States
- Prior art keywords
- photographic
- gelatin
- carboxymethylated
- binding agent
- hydrophilic colloids
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000084 colloidal system Substances 0.000 title abstract description 73
- 239000000463 material Substances 0.000 title description 15
- 239000000839 emulsion Substances 0.000 abstract description 89
- 108010010803 Gelatin Proteins 0.000 abstract description 81
- 229920000159 gelatin Polymers 0.000 abstract description 81
- 239000008273 gelatin Substances 0.000 abstract description 81
- 235000019322 gelatine Nutrition 0.000 abstract description 81
- 235000011852 gelatine desserts Nutrition 0.000 abstract description 81
- 239000011230 binding agent Substances 0.000 abstract description 49
- 108090000623 proteins and genes Proteins 0.000 abstract description 49
- 102000004169 proteins and genes Human genes 0.000 abstract description 49
- 229910052709 silver Inorganic materials 0.000 abstract description 46
- 239000004332 silver Substances 0.000 abstract description 46
- 238000012545 processing Methods 0.000 abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 82
- -1 silver halide Chemical class 0.000 description 52
- 235000018102 proteins Nutrition 0.000 description 48
- 229920002401 polyacrylamide Polymers 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 238000000576 coating method Methods 0.000 description 31
- 239000011248 coating agent Substances 0.000 description 26
- 238000005299 abrasion Methods 0.000 description 19
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 19
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 9
- 239000000975 dye Substances 0.000 description 8
- 150000004676 glycans Chemical class 0.000 description 8
- 239000004848 polyfunctional curative Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229920001282 polysaccharide Polymers 0.000 description 8
- 239000005017 polysaccharide Substances 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 6
- 230000001747 exhibiting effect Effects 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 3
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 3
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 108010088751 Albumins Proteins 0.000 description 2
- 102000009027 Albumins Human genes 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002307 Dextran Polymers 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 108010073771 Soybean Proteins Proteins 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000019710 soybean protein Nutrition 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- WICCYSZGCBTHGG-UHFFFAOYSA-N 1,3-benzoxazole pyrazol-3-one Chemical class N1=NC(C=C1)=O.O1C=NC2=C1C=CC=C2 WICCYSZGCBTHGG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 108700000434 Cannabis sativa edestin Proteins 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 108010044091 Globulins Proteins 0.000 description 1
- 102000006395 Globulins Human genes 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 108010058846 Ovalbumin Proteins 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000021120 animal protein Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- YGZZDQOCTFVBFC-UHFFFAOYSA-L disodium;1,5-dihydroxypentane-1,5-disulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C(O)CCCC(O)S([O-])(=O)=O YGZZDQOCTFVBFC-UHFFFAOYSA-L 0.000 description 1
- DHHNSJJTDFVVSG-UHFFFAOYSA-L disodium;benzene-1,4-diol;sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O.OC1=CC=C(O)C=C1 DHHNSJJTDFVVSG-UHFFFAOYSA-L 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- SYUXAJSOZXEFPP-UHFFFAOYSA-N glutin Natural products COc1c(O)cc2OC(=CC(=O)c2c1O)c3ccccc3OC4OC(CO)C(O)C(O)C4O SYUXAJSOZXEFPP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940070376 protein Drugs 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- SHNJHLWLAGUBOV-UHFFFAOYSA-N sodium;oxido(oxo)borane;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Na+].[O-]B=O SHNJHLWLAGUBOV-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical class NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
- G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
Definitions
- This invention relates to photographic materials, their preparation and use. In one of its aspects, this invention relates to a means for obtaining photographic emulsions and elements having improved photographic and physical properties. In another of its aspects, this invention relates to improved photographic silver halide emulsions and elements containing a unique combination of at least three hydrophilic colloids.
- gelatin a hydrophilic colloid
- organic hydrophilic colloids such as water soluble polyacrylamides have been used to improve the contrast of silver halide emulsions.
- emulsion layers containing such materials tend to have reduced resistance to abrasion. Good resistance to abrasion is, of course, very desirable in ph0tographic materials which are subjected to abrasion during handling, and particularly during processing in automatic processing equipment.
- carboxymethylated proteins have also been used as the sole replacement for part of the gelatin in binding agents to obtain improved photographic properties such as improved sensitivity and contrast.
- this has not achieved a combination of good speed and contrast with high resistance to abrasion, which is particularly desirable in photographic materials intended for processing in automatic processing equipment, e.g., equipment of the type described in Russell et al. U.S. Pat. 3,147,090, issued Sept. 1, 1964, and U.S. Pat. 3,025,779, issued Mar. 20, 1962.
- Another object of this invention is to provide a means for obtaining photographic emulsions and elements exhibiting an improved combination of photographic sensitivity and contrast together with good resistance to abrasion.
- Another object of this invention is to provide photographic elements which, due to their improved resistance to abrasion, are particularly suited for processing in automatic processing equipment.
- Still another object of this invention is to provide photographic silver halide emulsions and elements having a binding agent comprising a unique combination of gelatin and at least two other hydrophilic colloids.
- Still another object of this invention is to provide photographic elements having a unique binding agent and arrangement of layers which makes it possible to obtain improved photographic and physical properties.
- Still another object of this invention is to provide a photographic element containing a gelatin silver halide emulsion layer which can be processed to high speed and contrast in automatic processing equipment and which layers are resistant to abrasion and other physical imperfections.
- One embodiment of this invention relates to a photographic silver halide emulsion having a binding agent comprising gelatin and at least two other hydrophilic colloids, one of said other hydrophilic colloids being carboxymethylated protein at a concentration in the range of about 2.5 to about by weight, based on binding agent.
- Another embodiment of this invention relates to a photographic element comprising a support and a layer having a binding agent comprising gelatin and at least two other hydrophilic colloids, one of said other hydrophilic colloids being carboxymethylated protein at a concentration in the range of about 2.5 to about 50%, by weight, based on binding agent.
- Another embodiment of this invention relates to a photographic element comprising (1) a support, (2) a photographic silver halide emulsion layer having a binding agent comprising gelatin and at least two other hydro philic colloids, one of said other hydrophilic colloids being carboxymethylated protein at a concentration in the range of about 2.5 to about 50%, by weight, based on binding agent and (3) contiguous to said emulsion layer, a layer having a binding agent comprising gelatin and at least two other hydrophilic colloids, one of said other hydrophilic colloids being carboxymethylated protein at a concentration in the range of about 2.5 to about 50%, by weight, based on binding agent.
- Another embodiment of this invention relates to a photographic element comprising (1) a support, (2) a photographic silver halide emulsion layer having a binding agent comprising gelatin and about 2.5 to about 50%, by weight, of carboxymethylated protein and, (3) a layer which is contiguous to said emulsion layer and has a binding agent comprising gelatin and a different hydrophilic colloid other than carboxymethylated protein.
- Still another embodiment of this invention relates to a photographic element comprising (1) a support, (2) a photographic silver halide emulsion layer having a binding agent comprising gelatin and a different hydrophilic colloid other than carboxymethylated protein and, (3) a layer which is contiguous to said emulsion layer which has a binding agent comprising gelatin and about 2.5 to about 50%, by Weight, of carboxymethylated protein.
- hydrophilic colloids other than gelatin must be used together with gelatin in order to obtain the improved combination of properties described herein. This is evident from an examination of the following working examples, particularly Examples 1 and 2. Although hydrophilic colloids such as water soluble polyacrylamides have been used in binding agents to improve contrast, it could not have been expected that such materials could be used in combination with carboxymethylated proteins and gelatin to obtain a product which exhibits good photographic characteristics and resistance to abrasion.
- the binding agent or vehicle employed in the practice of this invention comprises gelatin, which is a hydrophilic colloid, and at least two hydrophilic colloids other than gelatin.
- gelatin which is a hydrophilic colloid, and at least two hydrophilic colloids other than gelatin.
- a portion, usually about 40 to about 95%, by Weight, of the gelatin generally used in photographic emulsions and elements is replaced by at least two different hydrophilic colloids.
- One of the hydrophilic colloids employed for this purpose is a carboxymethylated protein.
- Carboxymethylated prO- teins which can be employed in the practice of this invention include those described in Gates et al. US. Pat. 3,011,890, issued Dec. 5, 1961.
- Some of the naturally occurring amino containing vegetable and animal proteins which can be carboxymethylated and used in practicing this invention include, for example, soybean protein, casein, edestin, glutin, blood albumin, egg albumin, caster bean protein, globulin, and the like.
- the carboxymethylation of such proteins can be conveniently accomplished by reaction upon the protein with an alpha halo fatty acid such as bromoacetic acid at a pH of 912, such as is obtained by the presence of an alkaline buffer material in the reaction mass.
- the degree of carboxymethylation is subject to variation but will usually be in the range of about to about by weight.
- Many proteins such as gelatin can ordinarily be carboxymethylated without any prior treatment and used in practicing this invention.
- carboxymethylated protein contains naturally occurring sulfur compounds which are desirably destroyed or removed by oxidation prior to carboxymethylation.
- a suitable method which can be used for this purpose is treatment with hydrogen peroxide, as described in Lowe et al. US. Pat. 2,691,582, issued Oct. 12, 1954.
- concentrations of carboxymethylated protein employed in practicing this invention is subject to wide variation and will, of course, depend upon the concentration of gelatin and other hydrophilic colloid. However, satisfactory results can generally be obtained with concentrations in the range of about 2.5 to about 50%, by weight, based on total binding agent.
- the carboxymethylated protein is used in combination with a different hydrophilic colloid other than gelatin.
- the carboxymethylated protein comprises about 10 to about 90%, preferably about to about 70%, by weight, of the hydrophilic colloids other than gelatin in the binding agent.
- the combination of hydrophilic colloids other than gelatin is a mixture of a carboxymethylated protein, e.g., carboxymethylated casein, with a water soluble vinyl polymer, e.g., polyacrylamide.
- a third ingredient of the binding agent is a hydrophilic colloid which is different from both the gelatin and the carboxymethylated protein.
- This hydrophilic colloid contains substantially no free amino or carboxy groups and is compatible with gelatin.
- the preferred hydrophilic colloid which is different from both the gelatin and the carboxymethylated protein is preferably a water soluble vinyl polymer such as a water soluble polyacrylamide. While particularly efiicacious resuts are obtained with water soluble polyacrylamide, other hydrophilic colloids can be used in the binding agent with carboxymethylated protein and gelatin.
- Such other hydrophilic colloid which can be employed with gelatin, and the carboxymethylated protein and with or in place of the preferred polyacrylamide, include any of the hydrophilic water permeable colloids, particularly the materials generally employed in the preparation of photographic silver halide emulsions as binding materials or vehicles, as examplified by colloidal albumin, cellulose derivatives, synthetic resins, particularly water soluble vinyl polymers and the like.
- Specific examples include water soluble polymers such as polysaccharides, e.g., dextran, as disclosed in US. Pat. 3,063,838, issued Nov. 13, 1962, vinyl polymers, e.g., poly-N-vinyl pyrollidones, as disclosed in US. Pat.
- polyvinyl alcohol derivatives e.g., acid derivatives such as succinoylated polyvinyl alcohol, as disclosed in Minsk and Abel US. Pat. 3,165,412, issued Jan. 12, 1965, proteins, protein derivatives, as described in US. Pat. 2,852,- 382, issued Sept. 16, 1958, cellulose derivatives, e.g., hydroxyetheyl cellulose, as disclosed in Illingsworth and Minsk U.S. Pat. 3,003,878, issued Oct. 10, 1961, and like compounds.
- Additional hydrophilic colloids that can be used in the practice of this invention are polymers containing repeating units having the following formula:
- R is a carbon chain of 1 to 5 carbon atoms substituted with 1-3 substituents having the formula -COXR2R3, X being R being hydrogen or lower alkyl, and R and R each being hydrogen or alkyl groups containing up to 5 carbon atoms, alkoxy substituted alkyl groups containing up to 5 carbon atoms or hydroxy substituted alkyl groups containing up to 5 carbon atoms.
- Preferred polymers of this type contain repeating units having the following formula:
- Polymers of this type can also include monomeric units such as vinyl alcohol or other vinyl monomeric units including those represented by the formula:
- the reaction of the isocyanato compound with the poly(vinyl alcohol) may be partial or complete, as may be the reaction of the amine With the initial reaction product.
- a polymer of this type which can be employed in the practice of this invention is one which contains, in combined form, monomeric units of vinyl alcohol, vinyl carboxymethyl carbamate and vinyl -N ,8 hydroxyethylcarbamyl methylcarbamate.
- concentration of hydrophilic colloid (not including gelatin and carboxymethylated protein) employed in the practice of this invention is subject to wide variation. However, the most suitable concentrations are generally in the range of about 2.5 to about 50, preferably about 30 to about 70%, by weight, based on the weight of the binding agent.
- the carboxymethylated protein and hydrophilic colloid other than gelatin can be employed in one or more gelatin containing layers of a photographic silver halide element, including a gelatin, photographic silver halide emulsion layer.
- concentration of carboxymethylated protein and hydrophilic colloid other than gelatin, based on total binding agent, is generally in the range of about to about 60%, by weight.
- a mixture of carboxymethylated protein with the other hydrophilic colloid is employed in photographic elements in gelatin photographic silver halide layers and/or other gelatin layers which are contiguous or adjacent to the photographic silver halide layer.
- the carboxymethylated protein in one layer of a photographic element, e.g., in a gelatin photographic silver halide layer, and then use the other hydrophilic colloid in a contiguous or adjacent layer.
- This contiguous or adjacent layer can be between the carboxymethylated protein containing layer and the support or farther from the support.
- this latter arrangement of layers may be preferred to using both the carboxymethylated casein and other hydrophilic colloid with gelatin in a single layer.
- the water soluble polyacrylamides are the preferred polymeric hydrophilic colloids employed with gelatin and the carboxymethylated proteins in practicing this invention.
- Water soluble polyacrylamides can be obtained by polymerizing monomeric acrylamide using any procedure found suitable for this purpose. Typical methods for preparing water soluble polyacrylamides are described in Minsk et al. U.S. Pat. 2,486,191, issued Oct. 25, 1949; Lowe et al. U.S. Pat. 2,541,474, issued Feb. 13, 1951; U.S. Pat. 2,533,166, issued Dec. 5, 1950, and Allentolf et al. Belgian Pat. 651,507, issued Aug. 31, 1964.
- water soluble polyacrylamides are characterized by a temperature below which their solutions in water precipitate polyacrylamide. Therefore, to get solubility, some of these compounds must be dissolved in water at elevated temperatures. In general, however, grams of water soluble polyacrylamide will dissolve in one liter of water at 100 F.
- the polyacrylamides can contain, in combined form, not only acrylamide groups but also acrylic acid or acrylamide groups, depending upon their process of preparation.
- the inherent viscosity of the water insoluble polyacrylamides employed in the practice of this invention is subject to variation but is preferably in the range of about 0.1 to about 0.6, as determined at 25 C. in water. As used herein, the term inherent viscosity is determined by the formula:
- 1 is the inherent viscosity, is the relative viscosity of water solution of the polymer divided by the viscosity of the water in the same units and at the same temperature and c is the concentration in grams (0.25) for a polymer per 100 cc. of solution.
- any of the gelatin, photographic silver halide emulsions can be employed in practicing this invention, including, for example, photographic silver halide emulsions used in X-ray and camera films and the like.
- Suitable photographic emulsions contain silver halides such as silver chloride, silver bromide, silver bromoiodide, silver chloroiciiide, silver chlorobromide and the like.
- Photographic emulsions which form latent images predominantly within the silver halide grains can be usefully employed in the practice of this invention.
- Such internal latent image emulsions are disclosed in Davey and Knott U.S. Pat. 2,592,250, issued Apr. 8, 1952. Particularly good results are obtained with silver bromoiodide emulsions in which the average grain size of the silver bromoiodide crystals is in the range of about 0.5 to about 5 microns.
- the photographic compositions described herein can be coated on a wide variety of supports in preparing photographic elements.
- the photographic silver halide emulsions can be coated on one or both sides of the support which is preferably transparent and/or flexible.
- Typical supports are cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polyethylene, terephthalate film and other polyester film as well as glass, paper, metal, wood and the like.
- Supports such as paper which are coated with tit-olefin polymers, particularly polymers of u-olefins containing two or more carbon atoms, as exemplified by polyethylene, polypropylene, ethylenebutene copolymers, and the like, give good results.
- the photographic emulsions described herein can be chemically sensitized with compounds of the sulfur group, noble metal salts such as gold salts, reduction sensitized with reducing agents, and combinations of these.
- emulsion layers and other layers present in photographic elements made according to this invention can be hardened with any suitable hardener such as aldehyde hardeners, aziridine hardeners, hardeners which are derivatives of dioxane, oxypolysaccharides such as oxystarch, oxy plant gums, inorganic hardeners such as chromium salts, and the like.
- the photographic silver halide emulsions can also contain additional additives, particularly those known to be beneficial in photographic emulsions.
- the emulsion can contain speed increasing compounds, for example, onium salts, such as quaternary ammonium or ternary sulfonium salts, polyalkylene glycols, thioethers, and the like.
- the photographic silver halide emulsions can be stabilized with mercury compounds, azaindenes, quaternary benzothiazolium compounds, hydroxy substituted aromatic compounds, and the like.
- the photographic silver halide emulsions disclosed herein can also contain non-ionic, anionic and/or amphoteric coating aids.
- Some useful coating aids include, for example, saponin, alkyl substituted aryl oxy alkylene ethyl sulfonates of the type described in U.S. Pat. 2,600,- 831, issued June 17, 1952, maleoprimarates of the type described in U.S. Pat. 2,823,123, issued Feb. 11, 1958, taurine derivatives of the type described in U.S. Pat. 2,739,891, issued Mar. 27, 1956, and alkyl aminopropionates of the type described in U.S. Pat. 3,133,816, issued May 19, 1964.
- the emulsions and photographic elements described herein can contain incorporated developing agents such as polyhydroxy benzenes, aminophenols and 1,3-pyrazolidones.
- the photographic emulsions can also contain spectral sensitizers such as cyanines, merocyanines, complex (tri-nuclear) cyanines and complex (trinuclear) merocyanines, styryls and hemicyanines.
- cyanines, merocyanines, complex (tri-nuclear) cyanines and complex (trinuclear) merocyanines, styryls and hemicyanines can be blue sensitive emulsions or they can be orthochromatic, panchromatic or X-ray emulsions. 4
- the photographic silver halide elements described herein can contain absorbing dyes in the emulsion layer or in an auxiliary layer such as a layer coated between the support and the emulsion layer or the absorbing dyes can be included in both the emulsion and the auxiliary layer.
- These elements can also contain inert particles such as those often employed as matting agents in photographic elements. Suitable materials of this type include, for example, particles of silicon dioxide, glass, starch, polymethyl methacrylate, and the like. Such inert particles are often included in an emulsion layer and/or auxiliary layers coated over and/ or under an emulsion layer.
- the photographic layers described herein exhibit an improved combination of properties, including good resistance to abrasion.
- the resistance to abrasion for the coated samples reported in the following examples is determined by drawing a pointed stylus slowly across the surface of the coating swollen with developer and recording the grams pressure required to puncture the surface.
- Photographic speed (sensitivity), as reported in the following tables, is indicated as a function of the exposure necessary to give a density of 0.20 above background fog and is relative with respect to the control in each case.
- the silver bromoiodide emulsion is coated over a gelatin layer containing about 450 mg. of gelatin per square foot support. Over the silver bromoiodide emulsion layer is coated a gelatin layer containing about 150 mg. of gelatin per square foot of support.
- This sample (Coating No. 1) contains only gelatin as the binding agent and serves as the control.
- the resistance to abrasion for the samples is determined using the procedure described hereinbefore.
- the speed, gamma and net fog are also determined for the coated samples. The results are as follows:
- carboxymethylated proteins such as carboxymethylated gelatin, carboxymethylated soybean protein, and the like.
- water soluble polyacrylamide can be replaced in the above procedure by other hydrophilic colloids, such as hydro-xy ethyl cellulose, polyvinylpyrrolidone, succinoylated polyvinyl alcohol, dextran, and the like.
- carboxymethylated casein it is also possible to incorporate the carboxymethylated casein into the emulsion layer and put the polyacrylamide in the gelatin overcoat or undercoat.
- the carboxymethylated casein can be put in the gelatin overcoat or undercoat and the polyacrylamide put into the emulsion layer.
- absorbing dyes can also be achieved by adding materials such as absorbing dyes.
- materials such as absorbing dyes.
- a yellow sulfonated benzoxazole pyrazolone absorbing dye of the type disclosed in Heseltine US. Pat. No. 3,148,187, issued Sept. 8, 1964, is added to the emulsion layer in Coating 6 of the above procedure, there is obtained a photographic element having better image sharpness than a similar coating in which the absorbing dye is omitted.
- the absorbing dye can be added to the emulsion layer, even though it diffuses into the gelatin undercoat during coating.
- the dye can be coated at any suitable coverage, e.g., 4 mg. of absorbing dye per square foot of support.
- EXAMPLE 2 A coarse grained gelatino silver bromoiodide emulsion of the type normally used in medical X-ray film is coated on a conventional polyethylene film support.
- the coating contains mucochloric acid and chrome alum hardeners and an al-kyl substituted aryl oxy alkylene ethyl sulfonated coating aid.
- the silver bromoiodide emulsion is coated at a coverage of 430 mg. of silver and 410 mg. of gelatin per square foot of support.
- Over the silver bromoiodide emulsion is coated a gelatin layer containing approximately 150 mg. of gelatin per square foot of support.
- Carboxymethylated casein prepared as described in Gates et al. US. Pat.
- the combination of hydrophilic colloids including a carboxymethylated protein can be incorporated into a gelatin layer which is coated over an emulsion layer.
- a coarse grained gelatino silver bromoiodide emulsion of the type normally used in medical X-ray film is coated on conventional cellulose acetate film support.
- the emulsion coating contains mucochloric acid and chrome alum hardeners and an alkyl substituted aryl oxy ethyl sulfonated coating aid.
- the silver bromoiodide emulsion is coated at a coverage of 390 mg. of silver and 660 mg. of gelatin per square foot of support.
- Over the emulsion layer is coated a gelatin layer containing about mg. of gelatin per square foot of support.
- This photographic element (Coating No. 1) contains only gelatin as the binding agent and serves as the control.
- Another coating (Coating No. 2) is prepared using the above procedure except that the gelatin layer coated over the emulsion layer contains both carboxymethylated casein, prepared as described in Gates et al. U.S. Pat. 3,011,890, issued Dec. 5, 1961, and polyacrylamide (inherent viscosity of 0.30 in water at 25 C.).
- the coverages in the gelatin layer over the emulsion layer are 91 mg. of gelatin per square foot of support, .13 mg. of carboxymethylated casein per square foot of support and 13 mg. of polyacrylamide per square foot of support.
- samples of each coating are also tested for static resistance.
- the coatings Prior to exposure, the coatings are conditioned at -30% relative humidity and put in contact with an X-ray fluorescent screen and rolled under a pressure of 30 pounds per square inch. The screen and film samples are then separated and discharged by contacting with a grounded 90 metal frame which gives a well defined static pattern. After development, the samples are visually observed and assigned a static resistance number from 0-10, 0 indicating no static with increasing degrees of static being given a progressively higher number.
- Coating 1 is rated at 7, indicating a moderate to heavy static pattern while Coating 2 is rated at 5, indicating a much greater resistance to static.
- photographic silver halide emulsions and elements exhibiting an improved combination of photographic and physical properties.
- This invention enables one skilled in the art to take advantage of the improved physical properties, for example, resistance to abrasion, without substantially down-grading photographic properties such as sensitivity and contrast.
- the photographic elements described herein, by virtue of their excellent combination of physical and photographic properties, are particularly useful for processing in automatic equipment.
- a photographic silver halide emulsion having a binding agent comprising gelatin and at least two other hydrophilic colloids, one of the said other colloids being carboxymethylated protein at a concentration in the range of about 2.5 to about 50%, by weight, based on binding agent, and the other of said hydrophilic colloids being compatible with gelatin and selected from the group consisting of a polyacrylamide, polysaccharides, and poly-N- vinyl pyrrolidone.
- hydrophilic colloids comprise a mixture of carboxymethylated casein with a water soluble polyacrylamide having an inherent viscosity in the range of about 0.1 to about 0.6.
- a photographic element comprising a support and a layer having a binding agent comprising gelatin and at least two other hydrophilic colloids, one of said other hydrophilic colloids being carboxymethylated protein at a concentration in the range of about 2.5 to about 50%, by weight, based on binding agent, and the other of said hydrophilic colloids being compatible with gelatin and selected from the group consisting of 21 polyacrylamide, polysaccharides, and poly-N-vinyl pyrrolidone.
- hydrophilic colloids comprise a mixture of carboxymethylated casein with water soluble poly-N-vinyl pyrrolidone.
- hydrophilic colloids comprise a mixture of carboxymethylated casein with a water soluble polyacrylamide having an inherent viscosity in the range of about 0.1 to about 0.6.
- a photographic element comprising (1) a support, (2) a photographic silver halide emulsion layer having a binding agent comprising gelatin and at least two other hydrophilic colloids, one of said other hydrophilic colloids being carboxymethylated protein at a concentration in the range of about 2.5 to about 50% by weight, based on binding agent, and the other of said hydrophilic colloids being compatible with gelatin and selected from the group consisting of a polyacrylamide, polysaccharides, and poly-N-vinyl pyrrolidone and (3) contiguous to said emulsion layer, a layer having a binding agent comprising gelatin and at least two other hydrophilic colloids, one of said other hydrophilic colloids, being carboxymethylated protein at a concentration in the range of about 2.5 to about 50%, by weight, based on binding agent, and selected from the group consisting of a polyacrylamide, polysaccharides, and poly-N-vinyl pyrrolidone.
- the layer having a binding agent comprising gelatin and at least two other hydrophilic colloids is a layer which is contiguous to a photographic silver halide emulsion layer and is farther from the support than said emulsion layer.
- a photographic element comprising (1) a support, (2) a photographic silver halide emulsion layer having a binding agent comprising gelatin and about 2.5 to about 50%, by weight, of carboxymethylated protein and (3) a layer which is contiguous to said emulsion layer and has a binding agent comprising gelatin and a different hydrophilic colloid other than carboxymethylated protein selected from the group consisting of 21 polyacrylamide, polysaccharides, and poly-N-vinyl pyrrolidone.
- a photographic element comprising (1) a support, (2) a photographic silver halide emulsion layer having a binding agent comprising gelatin and a different hydrophilic colloid other than carboxymethylated protein selected from the group consisting of a polyacrylamide, polysaccharides, and poly-N-vinyl pyrrolidone and, (3) a layer which is contiguous to said emulsion layer and has a binding agent comprising gelatin at about 2.5 to about 50%, by weight, of carboxymethylated protein.
- hydrophilic colloid in (3) is water soluble polyacryl- 1 l amide having an inherent viscosity in the range of about 0.1 to about 0.6.
- hydrophilic colloid in (2) is water soluble polyacrylamide having an inherent viscosity in the range of about 0.1 to about 0.6.
- a photographic element comprising (1) a support, (2) a photographic silver halide emulsion layer and (3) a layer which is contigous to said emulsion layer and has a binding agent comprising gelatin and has at least two other hydrophilic colloids, one of said other hydrophilic colloids being carboxymethylated protein at a concentration in the range of about 2.5 to about 50%, by weight, based on binding agents, and the other of said hydrophilic colloids being compatible with gelatin and selected from the group consisting of a polyacrylamide, polysaccharides, and poly-N-vinyl pyrrolidone.
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- Chemical Kinetics & Catalysis (AREA)
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Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US50683165A | 1965-11-08 | 1965-11-08 |
Publications (1)
Publication Number | Publication Date |
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US3589908A true US3589908A (en) | 1971-06-29 |
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Family Applications (1)
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US506831A Expired - Lifetime US3589908A (en) | 1965-11-08 | 1965-11-08 | Photographic materials containing hydrophilic colloids |
Country Status (5)
Country | Link |
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US (1) | US3589908A (enrdf_load_stackoverflow) |
BE (1) | BE689373A (enrdf_load_stackoverflow) |
DE (1) | DE1547745C3 (enrdf_load_stackoverflow) |
FR (1) | FR1498880A (enrdf_load_stackoverflow) |
GB (1) | GB1164830A (enrdf_load_stackoverflow) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5041364A (en) * | 1990-10-01 | 1991-08-20 | Eastman Kodak Company | Diagnostic photographic elements exhibiting reduced glare following rapid access processing |
EP0790526A1 (en) | 1996-02-19 | 1997-08-20 | Agfa-Gevaert N.V. | Radiographic image forming film-screen system |
US5674671A (en) * | 1994-07-18 | 1997-10-07 | Minnesota Mining And Manufacturing Company | Light senitive material having improved antistatic behavior |
-
0
- BE BE689373D patent/BE689373A/xx unknown
-
1965
- 1965-11-08 US US506831A patent/US3589908A/en not_active Expired - Lifetime
-
1966
- 1966-11-07 DE DE1547745A patent/DE1547745C3/de not_active Expired
- 1966-11-08 GB GB49933/66A patent/GB1164830A/en not_active Expired
- 1966-11-08 FR FR82861A patent/FR1498880A/fr not_active Expired
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5041364A (en) * | 1990-10-01 | 1991-08-20 | Eastman Kodak Company | Diagnostic photographic elements exhibiting reduced glare following rapid access processing |
US5674671A (en) * | 1994-07-18 | 1997-10-07 | Minnesota Mining And Manufacturing Company | Light senitive material having improved antistatic behavior |
EP0790526A1 (en) | 1996-02-19 | 1997-08-20 | Agfa-Gevaert N.V. | Radiographic image forming film-screen system |
Also Published As
Publication number | Publication date |
---|---|
DE1547745A1 (de) | 1969-11-20 |
DE1547745C3 (de) | 1980-04-03 |
FR1498880A (fr) | 1967-10-20 |
DE1547745B2 (de) | 1979-07-26 |
BE689373A (enrdf_load_stackoverflow) | |
GB1164830A (en) | 1969-09-24 |
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